Thermal Decomposition Kinetics of Dicyclopentadiene‐1,8‐dione: The Reaction Path through Quantum Chemical Calculation

Thermal decomposition kinetics of dicyclopentadiene‐1,8‐dione 7 implied an intramolecular competition between α,β‐ and β,γ‐double bond to assist the CO elimination. Experimental thermolysis of 7 in dioxane gave 3a,7a‐dihydro‐1H‐inden‐1‐one (cis‐bicyclo[4.3.0]nona‐2,4,7‐triene‐9‐one), CO gas, and a very small amount of indanone. This result suggested β,γ‐double bond favored the extrusion of CO gas. Calculations of several density functional theory (DFT) levels of theory and CBS‐QB3 method were employed. Two mechanisms were considered: a one‐step concerted pathway and a stepwise mechanism involving [1,3] and [1,5] hydrogen sigmatropic migrations. The CAM‐B3LYP/6‐31G(d,p) calculation reasonably agrees with the experimental kinetic parameters. The mechanism appears to be unimolecular in one step concerted through a five‐membered cyclic transition state. Isomerization of product cis‐bicyclo[4.3.0]nona‐2,4,7‐triene‐9‐one yielding 1‐indanone is presented and described. Calculation from substrate 7 may explain in a similar way the mechanism of decomposition of compounds 1‐6 . The present work may well promote to the possibility of carrying out experimental research works on the thermal decarbonylation kinetics in a liquid solution and in the gas phase of β,γ‐unsaturated aliphatic ketones.     

Homogeneous catalysis on the gas-phase dehydration reaction of tertiary alcohols by hydrogen bromide. Density functional theory calculation

The gas-phase thermal dehydration mechanism of tert-butanol, 2-methyl-2-butanol, 2-methyl-2-pentanol and 2,3-dimethyl-2-butanol by homogeneous catalysis of hydrogen bromide was examined by density functional theory calculations with the hybrid functionals: M062X, CAMB3LYP and WB97XD. Reasonable agreements were found between theoretical and experimental enthalpy values at the WB97XD/6-311++G(d,p) level. The dehydration mechanism of tert-butanol with and without catalysis was evaluated in order to examine the catalyst effect on the mechanism. The elimination reaction without catalysis involves a four-membered transition state (TS), while the reaction with catalysis involves a six-membered TS. The mechanism without catalysis has enthalpy activation over 150 kJ mol^–1 greater than the catalysed reaction. In all these reactions, the elongation of the C–O bond is significant in the TS. The un-catalysed reaction is controlled by breaking of C–O bond, and it was found to be more synchronous (Sy ≈ 0.91) than the hydrogen bromide catalysed reactions (Sy ≈ 0.75–0.78); the latter reactions are dominated by the three reaction coordinates associated with water formation. No significant effect on the enthalpies of activation was observed when the size of the alkyl chain was increased.     

Aerosol size standards in the nanometer size range II. Narrow size distributions of polystyrene 3-11 nm in diameter

A technique for generating charged aerosols of polystyrene (pSty) with narrow size distributions has been developed. It is based on electrospraying commercial narrow mass standards of pSty dissolved in l-methyl-2-pyrrolidone (NMP) seeded with the newly synthesized salt dimethyl ammonium formate. This salt imparts a much larger electrical conductivity than previously known NMP electrolytes, leading to higher quality sprays with greatly reduced attachment of impurities. Controlling the solute concentration enables forming polystyrene particles containing from one up to more than ten single polystyrene molecules, whereby 4 mass standards with molecular weights from 9200 up to 96,000 g/mol yield particles covering densely the diameter range from 3 to 11 nm. Combined mobility and mass measurement with a differential mobility analyzer and a mass spectrometer in tandem are carried out with a pSty sample 9200 amu in molecular weight. They fix directly the mass versus mobility relation near 9200 amu, and indirectly for the other standards and their clusters. The apparent particle density resulting from mobility versus mass data agrees with the bulk density of the polymer, indicating that the particles are dense and spherical. Although these standards have been studied only in gaseous suspension, their injection in liquids such as water where pSty is insoluble should keep them spherical.     

Stress regularity in quasi-static perfect plasticity with a pressure dependent yield criterion

This work is devoted to establishing a regularity result for the stress tensor in quasi-static planar isotropic linearly elastic – perfectly plastic materials obeying a Drucker–Prager or Mohr–Coulomb yield criterion. Under suitable assumptions on the data, it is proved that the stress tensor has a spatial gradient that is locally squared integrable. As a corollary, the usual measure theoretical flow rule is expressed in a strong form using the quasi-continuous representative of the stress.     

The Equilibrium Measure for a Nonlocal Dislocation Energy

In this paper we characterize the equilibrium measure for a nonlocal and anisotropic weighted energy describing the interaction of positive dislocations in the plane. We prove that the minimum value of the energy is attained by a measure supported on the vertical axis and distributed according to the semicircle law, a well-known measure that also arises as the minimizer of purely logarithmic interactions in one dimension. In this way we give a positive answer to the conjecture that positive dislocations tend to form vertical walls. This result is one of the few examples where the minimizer of a nonlocal energy is explicitly computed and the only one in the case of anisotropic kernels. © 2018 Wiley Periodicals, Inc.     

Synthesis of Symmetrical and Nonsymmetrical Polyenes by Iterative and Bidirectional Palladium-Catalyzed Cross-Coupling Reactions

Bifunctional unsaturated reagents designed to undergo palladium-catalyzed cross-coupling reactions with complementary polyenyl connective fragments are highly useful for the undoubtedly challenging synthesis of polyenes. The current toolkit of building blocks for the bidirectional formation of Csp²−Csp² single bonds of polyenes includes homo-bisfunctionalized reagents with equal or unequal reactivity (due to steric and/or electronic factors), and hetero-bisfunctionalized counterparts containing either two different nucleophiles, two electrophiles or one of these functionalities and a latent nucleophile that can be unmasked when desired. The combination of these bifunctional linchpin reagents using tactics that modulate the reactivity of each terminus in order to achieve the required connection have streamlined the synthesis of polyenes of great complexity using (iterative) cross-coupling methods for Csp²−Csp² bond formation. Reaction conditions for the Pd-catalyzed cross-coupling reactions are mild and functional-group-tolerant, and therefore these protocols allow to construct the polyene structures using shorter unsaturated reactants with the desired geometries, since in general the products preserve the stereochemical information of the connected cross-coupling partners.     

Analysis of Li distribution in ultrathin all-solid-state Li-ion battery (ASSLiB) by neutron depth profiling (NDP)

Lithium-ion batteries are promising energy storage technology devices. They possess many advantages, including high energy density, flexible and lightweight construction and considerable durability. The rapid development of nanotechnologies can further improve their capacity, cycle life and safety. In this experiment, Li-ion diffusion in an all-solid lithium-ion battery (ASSLiB) was studied using the Neutron Depth Profiling (NDP) nuclear analytical technique. The thin ASSLiB system was synthesised by RF magnetron sputtering. The experiment showed that NDP is a very efficient experimental tool for direct analysis of Li distribution in Li batteries. It has been found that the depth profile of Li strongly depends on the state of charge of the battery. About one-third of the total number of Li in ASSLiB can move between the electrodes during charging / discharging. It has been also shown, using the multipixel detectors, that the lateral distribution of Li in ASSLiB is not homogeneous. This can mean, for example, that the position of Li is affected by structural defects that may arise due to variation of the volume or stress of the battery during charging or discharging. In the work are presented first results of measurements performed on ASSLiB of a 1?µm thickness.